Proceedings of the Royal Society of London A Mathematical and Physical Sciences · 1963 · 70 citations · 7 references
Natural SciencesChemistryChemical KineticsInorganic ChemistryPhysical ChemistryChemical Reaction KineticsHydrogen AtomOxygen EvolutionReaction Mechanism AnalysisReactive Oxygen SpeciesRedox ChemistryChain Reaction KineticsChain Reaction MechanismsElementary Rate ProcessesKinetics Of Oxygen EvolutionNegative Temperature CoefficientRate-determining StepRate-determining Step AnalysisRedox Kinetics
Abstract The addition of molecular oxygen was found to increase the rate of rem oval of hydrogen atoms in a flow system at and below room temperature. Kinetic studies of this process using argon carrier showed that the rate-determining step is the third-order reaction H + O2 + Ar = HO2 + Ar. (2) Atomic oxygen in small concentrations is produced in the system. Product analysis and measurements of oxygen atom concentrations indicated that the principal reactions removing HO2 under these conditions are H+HO2 = H2+O2, (12a) H+HO2 = OH+OH, (12b) H+HO2 = H2O+O2, (12c) A value for k2 of 2.2 x 10-32 cm6 molecule-2 s-1 was determined at 293 °K. Reaction (2) was found to have a small negative temperature coefficient. These data and values of k2 from explosion limit studies can be represented by the expression k2 = 1.3 x 10-33 exp (+ 1600 + 700/RT) cm6 molecule-2 s-1 in the range 250 to 800 °K. The third-body efficiencies in reaction (2) at 293 °K of He and H2O relative to Ar are similar to those obtained from data on the second explosion limit at higher temperatures.
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